JP6102997B2 - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Description

  The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, and a liquid crystal display element.

  In recent years, liquid crystal display elements have advantages such as low power consumption and easy miniaturization and flattening. Therefore, liquid crystal display elements can be used from small liquid crystal display devices such as mobile phones to large screen liquid crystals such as liquid crystal televisions. It is applied to a wide range of uses up to display devices.

  As a driving mode of the liquid crystal display device, there are TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane Switching), VA (Vertical Alignment), etc. according to the change of the alignment (alignment) state of the liquid crystal molecules. Are known. In VA mode, MVA (Multi domain Vertical Alignment) method and PVA (Patterned Vertical Alignment) method are adopted to increase the viewing angle by orientation division, further improving the high-speed response and panel aperture ratio to the liquid crystal. It has been studied to adopt a pre-tilt angle for use in an optical vertical alignment method, a PSA (Polymer Sustained Alignment) method, and the like. In any of these drive modes, the alignment state of the liquid crystal molecules is directly controlled by the liquid crystal alignment film, and the liquid crystal alignment film is responsible for the development and control of the functional characteristics of the liquid crystal display element.

  Since such a liquid crystal display device is expected as a moving image display device such as a mobile phone or a liquid crystal television, as a characteristic required for a liquid crystal display element, an electro-optic effect is required to suppress an afterimage as much as possible while smoothly displaying a moving image. A further increase in response time is required. In response to this requirement, a technique for improving the structure by imparting a structure that gives dielectric anisotropy to the polymer side chain used in the liquid crystal alignment film has been reported (Japanese Patent Publication No. 2007-521361 and Japanese Patent Publication No. 2007-521506). No. publication). However, this patent document does not describe electrical characteristics such as a voltage holding ratio and an afterimage characteristic which are important in practical use other than speeding up the electro-optic response time.

  Under such circumstances, it is desired to develop a liquid crystal aligning agent capable of producing a liquid crystal display element excellent in various performances such as a voltage holding ratio while realizing a high-speed response of the liquid crystal element.

Special table 2007-521361 Special table 2007-521506 gazette

  The present invention has been made based on the above circumstances, the purpose of which can be a high-speed response, and can produce a liquid crystal display device excellent in voltage holding ratio, afterimage characteristics and light resistance, It is to provide a liquid crystal aligning agent that is excellent in uniform coating property.

（式（１）中、
Ｒ^１は、メチレン基、炭素数２〜３０のアルキレン基、−（Ｃ_ｂＨ_２ｂＯ）_ｃ−、フェニレン基又はシクロヘキシレン基である。ｂは、０〜２０の整数である。ｃは、０〜１０の整数である。但し、これらの基の水素原子の一部又は全部は、置換されていてもよい。
Ｒ^２は、炭素−炭素二重結合、炭素−炭素三重結合、エーテル結合、エステル結合又はアミド結合を含む連結基である。
Ｒ^３は、少なくとも２個の単環構造を有する基である。
ａは、０又は１の整数である。） The invention made to solve the above problems is
[A] contains at least one polymer selected from the group consisting of polyamic acid, polyimide, (meth) acrylic polymer, polysiloxane, and polyamic acid ester (hereinafter also referred to as “[A] polymer”). And the said polymer is a liquid crystal aligning agent which has group represented by following formula (1).

(In the formula (1),
R ¹ is a methylene group, an alkylene group having 2 to 30 carbon atoms, — (C _b H _2b O) _c —, a phenylene group or a cyclohexylene group. b is an integer of 0-20. c is an integer of 0-10. However, some or all of the hydrogen atoms of these groups may be substituted.
R ² is a linking group containing a carbon-carbon double bond, a carbon-carbon triple bond, an ether bond, an ester bond or an amide bond.
R ³ is a group having at least two monocyclic structures.
a is an integer of 0 or 1. )

  When the liquid crystal aligning agent contains the [A] polymer having a specific structure group represented by the above formula (1), a high-speed response can be realized. In addition, by appropriately selecting at least one polymer selected from the group consisting of polyamic acid, polyimide, (meth) acrylic polymer, polysiloxane, and polyamic acid ester having different polymer main chain structures, a liquid crystal display element can be used. Desired characteristics (voltage holding ratio, afterimage characteristics, uniform coatability, light resistance) can be imparted.

（式（２）中、
Ｒ^４及びＲ^６は、それぞれ独立してフェニレン基、ビフェニレン基、ナフタレン基、シクロヘキシレン基、ビシクロヘキシレン基、シクロへキシレンフェニレン基又は複素環である。但し、これらの基の水素原子の一部又は全部は、置換されていてもよい。
Ｒ^５は、メチレン基、炭素数２〜１０のアルキレン基、炭素−炭素二重結合、炭素−炭素三重結合、エーテル結合、エステル結合又は複素環を含む連結基である。但し、上記連結基の水素原子の一部又は全部は、置換されていてもよい。
Ｒ^７は、水素原子、シアノ基、フッ素原子、トリフルオロメチル基、アルコキシカルボニル基、アルキル基、アルコキシ基、トリフルオロメトキシ基又はアルキルカルボニルオキシ基である。
ｂは、０又は１である。ｃは、１〜９の整数である。但し、Ｒ^７が複数の場合、複数のＲ^７は同一でも異なっていてもよい。） R ³ is preferably a group represented by the following formula (2).

(In the formula (2),
R ⁴ and R ⁶ are each independently a phenylene group, a biphenylene group, a naphthalene group, a cyclohexylene group, a bicyclohexylene group, a cyclohexylenephenylene group, or a heterocyclic ring. However, some or all of the hydrogen atoms of these groups may be substituted.
R ⁵ is a linking group containing a methylene group, an alkylene group having 2 to 10 carbon atoms, a carbon-carbon double bond, a carbon-carbon triple bond, an ether bond, an ester bond or a heterocyclic ring. However, one part or all part of the hydrogen atom of the said coupling group may be substituted.
R ⁷ is a hydrogen atom, a cyano group, a fluorine atom, a trifluoromethyl group, an alkoxycarbonyl group, an alkyl group, an alkoxy group, a trifluoromethoxy group, or an alkylcarbonyloxy group.
b is 0 or 1. c is an integer of 1-9. However, when R ⁷ is plural, a plurality of R ⁷ may be the same or different. )

  [A] By introducing the structure represented by the above formula (2) as the side chain of the polymer, the response speed of the obtained liquid crystal alignment element can be further improved.

  The present invention preferably includes a liquid crystal alignment film formed from the liquid crystal display element and a liquid crystal display element including the liquid crystal alignment film. As described above, according to the liquid crystal aligning agent, it is possible to produce a liquid crystal display element capable of high-speed response and excellent in various performances such as voltage holding ratio, afterimage characteristics, uniform coating property, and light resistance. The liquid crystal display element can be suitably applied in driving modes such as TN, STN, IPS, FFS, Ht-VA (VA-IPS), and VA (including MVA, PVA, optical vertical alignment, PSA, and the like). .

  According to the present invention, a liquid crystal aligning agent capable of high-speed response and capable of producing a liquid crystal display element excellent in various performances such as voltage holding ratio, afterimage characteristics, light resistance and the like, and excellent in uniform coating property. Can be provided. Therefore, the liquid crystal display element can be suitably applied in driving modes such as TN, STN, IPS, FFS, Ht-VA (VA-IPS), and VA (including MVA, PVA, optical vertical alignment, PSA, and the like). it can.

<Liquid crystal aligning agent>
The liquid crystal aligning agent of this invention contains a [A] polymer. In addition, the liquid crystal aligning agent can contain other optional components as long as the effects of the present invention are not impaired. Hereinafter, each component will be described in detail.

<[A] polymer>
[A] The polymer contains at least one polymer selected from the group consisting of polyamic acid, polyimide, (meth) acrylic polymer, polysiloxane and polyamic acid ester, and the polymer is represented by the above formula ( It has group represented by 1). When the liquid crystal aligning agent contains the [A] polymer having a specific structure group represented by the above formula (1), a high-speed response can be realized. In addition, by appropriately selecting at least one polymer selected from the group consisting of polyamic acid, polyimide, (meth) acrylic polymer, polysiloxane, and polyamic acid ester having different polymer main chain structures, a liquid crystal display element can be used. Desired characteristics (voltage holding ratio, afterimage characteristics, uniform coatability, light resistance) can be imparted. Hereinafter, the group represented by the above formula (1) and the respective polymers will be described in detail.

[Group Represented by Formula (1)]
In the formula (1), ^{R 1} represents a methylene group, an alkylene group having 2 to 30 carbon _{atoms, - (C b H 2b O} ) c -, a phenylene group or a cyclohexylene group. b is an integer of 0-20. c is an integer of 0-10. However, some or all of the hydrogen atoms of these groups may be substituted. R ² is a linking group containing a carbon-carbon double bond, a carbon-carbon triple bond, an ether bond, an ester bond or an amide bond. R ³ is a group having at least two monocyclic structures. a is an integer of 0 or 1.

The linking group represented by R ² is preferably an ether group, an ester group, or an amide group.

Examples of the alkylene group having 2 to 30 carbon atoms represented by R ¹ include an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tetradecylene group, Hexadecylene group, octadecylene group, nonadecylene group, icosylene group, hencicosylene group, docosylene group, tricosylene group, tetracosylene group, pentacosylene group, hexacosylene group, heptacosylene group, octacosylene group, nonacosylene group, triaconylene group, etc. .

The group having at least two monocyclic structures represented by R ³ is preferably a group represented by the above formula (2). [A] By introducing the structure represented by the above formula (2) as the side chain of the polymer, the response speed of the obtained liquid crystal alignment element can be further improved.

In the above formula (2), R ⁴ and R ⁶ are each independently a phenylene group, a biphenylene group, a naphthalene group, a cyclohexylene group, a bicyclohexylene group, a cyclohexylenephenylene group, or a heterocyclic ring. However, some or all of the hydrogen atoms of these groups may be substituted. R ⁵ is a linking group containing a methylene group, an alkylene group having 2 to 10 carbon atoms, a carbon-carbon double bond, a carbon-carbon triple bond, an ether bond, an ester bond or a heterocyclic ring. However, one part or all part of the hydrogen atom of the said coupling group may be substituted. R ⁷ is a hydrogen atom, a cyano group, a fluorine atom, a trifluoromethyl group, an alkoxycarbonyl group, an alkyl group, an alkoxy group, a trifluoromethoxy group, or an alkylcarbonyloxy group. b is 0 or 1. c is an integer of 1-9. However, when R ⁷ is plural, a plurality of R ⁷ may be the same or different. In the present specification, the condensed ring such as the naphthalene group is included in a single ring.

Examples of the heterocyclic ring represented by R ⁴ and R ⁶ include a pyridine ring, a pyridazine ring, and a pyrimidine ring. Examples of the alkylene group having 2 to 10 carbon atoms of the linking group containing the alkylene group having 2 to 10 carbon atoms represented by R ⁵ include an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, and an octylene group. It is done. Examples of the heterocyclic ring represented by R ⁵ include a pyridine ring, a pyridazine ring, and a pyrimidine ring. Examples of the alkoxycarbonyl group represented by R ⁷ include a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group. Examples of the alkyl group represented by R ⁷ include linear or branched alkyl groups having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group, and an isobutyl group. Examples of the alkoxy group represented by R ⁷ include a methoxy group, an ethoxy group, and a propoxy group. Examples of the alkylcarbonyloxy group represented by R ⁷ include a methoxycarbonyloxy group, an ethoxycarbonyloxy group, and a propoxycarbonyloxy group.

From the viewpoint of high-speed response of a liquid crystal display device using the liquid crystal aligning agent, R ⁷ is preferably an alkyl group, and more preferably a linear alkyl group having 1 to 20 carbon atoms. Moreover, it is preferable that at least one group of R ^{4 to} R ⁶ has a fluorine atom.

  Examples of the group represented by the above formula (2) include a group represented by the following formula.

In the above formula (2-1) ~ (2-123), R 8 is an alkyl group or an alkoxy group having 1 to 20 carbon atoms. X is each independently a hydrogen atom or a fluorine atom.

R ⁸ is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms.

  As the group represented by the above formula (2), the above formula (2-1), formula (2-4), formula (2-6) from the viewpoint of high-speed response of the liquid crystal display element using the liquid crystal aligning agent ), Formulas (2-41), formulas (2-50) to (2-60), formulas (2-64), and groups represented by formulas (2-65) to (2-123) are preferred. A group having a fluorine atom and having an alkyl group at its terminal as in (2-41), formulas (2-50) to (2-58) and formulas (2-65) to (2-123) The group represented by formula (2-72) and the group represented by formula (2-90) are more preferred.

[Polyamic acid]
[A] The polyamic acid as a polymer is obtained by reacting a tetracarboxylic dianhydride with a diamine compound. A part of the diamine compound needs to be a diamine compound containing a group represented by the formula (1).

  Examples of tetracarboxylic dianhydrides include aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, aromatic tetracarboxylic dianhydrides, and the like. These tetracarboxylic dianhydrides can be used alone or in combination of two or more.

  Examples of the aliphatic tetracarboxylic dianhydride include butanetetracarboxylic dianhydride.

Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4. , 5,9b-Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b -Hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] Octane-2,4-dione-6-spiro-3 ′-(tetrahydrofuran-2 ′, 5′-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene -1,2-dicarboxylic acid Water, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-dianhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane- 2: 4,6: 8-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone and the like.

  Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride and the like, and the tetracarboxylic dianhydride described in Japanese Patent Application No. 2010-97188.

  Of these tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides are preferred, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride. Anhydrides are more preferred.

  Examples of the diamine compound include aliphatic diamine, alicyclic diamine, diaminoorganosiloxane, and aromatic diamine. These diamine compounds can be used alone or in combination of two or more.

  Examples of the aliphatic diamine include metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, and the like.

  Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 4,4′-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane, and the like.

  Examples of the diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and the like, and diamines described in Japanese Patent Application No. 2009-97188.

  Examples of the aromatic diamine include p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2′-dimethyl-4,4′-diaminobiphenyl. 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 2,7-diaminofluorene, 4,4′-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) Phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoro Propane, 4,4 ′-(p-phenylenediisopropylidene) bisaniline, 4,4 ′-(m-pheny Diisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4 -Diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole N, N′-bis (4-aminophenyl) -benzidine, N, N′-bis (4-aminophenyl) -N, N′-dimethylbenzidine, 1,4-bis- (4-aminophenyl)- Piperazine, 3,5-diaminobenzoic acid, dodecanoxy-2,4-diaminobenzene, tetradecanoxy-2,4-diamy Benzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, dodecanoxy-2,5-diaminobenzene, tetradecanoxy-2,5-diaminobenzene, pentadecanoxy-2 , 5-diaminobenzene, hexadecanoxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy- 2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholestenyl 3,5-diaminobenzoate, lanostannyl 3,5-diaminobenzoate, 3,6-bi (4-aminobenzoyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, 4- (4′-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (4 ′ -Trifluoromethylbenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 1,1-bis (4-(( Aminophenyl) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenoxy) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) ) Phenyl) -4- (4-heptylcyclohexyl) cyclohexane, 2,4-diamino-N, - diallyl aniline, 4-amino-benzylamine, 3-amino benzylamine compound represented by the following formula (3) include compounds represented by the following formula (4).

In the above formula (3), R ⁹ , R ^{9 ″} and R ^{9 ′ ″} are each independently a single bond, —O—, * —COO— or —OCO—. However, the R ⁹ * is a site which binds a diaminophenyl group. Moreover, * of R ^{9 ″} and R ^{9 ′ ″} is a site bonded to the phenylene group side. R ^{9 ′} is an alkanediyl group having 1 to 3 carbon atoms. d is 0 or 1. e is an integer of 0-2. f is 0 or 1. R ¹⁰ is a linear, branched or cyclic alkyl group. The two amino groups in the diaminophenyl group are preferably bonded to the 2,4 position or the 3,5 position.

In said formula (4), R < ⁹ >, d, and e are synonymous with the said Formula (3). R ¹ to R ³ and a are as defined in the above formula (1). The two amino groups in the diaminophenyl group are preferably bonded to the 2,4 position or the 3,5 position. g is an integer of 1-5.

About said R < ¹ > -R < ³ >, description of each definition in the said [group represented by Formula (1)] and description of a preferable group are applicable as it is.

  As said g, 1-3 are preferable from a viewpoint of the high-speed response of the liquid crystal display element using the said liquid crystal aligning agent, and 2 or 3 is more preferable.

  Examples of the diamine represented by the above formula (4) include diamines represented by the following formula.

  Among these diamines, in the case of selecting a polyamic acid as the [A] polymer, from the viewpoint of introducing the group represented by the above formula (1) into the polymer, at least the above formula ( It is necessary to use a diamine having a group represented by the formula (1) such as a compound represented by 4). In addition, when using other diamine together, it is preferable to use the compound represented by the said Formula (3).

  The ratio of the tetracarboxylic dianhydride and the diamine compound used in the polyamic acid synthesis reaction is such that the acid anhydride group of the tetracarboxylic dianhydride is 0 with respect to 1 equivalent of the amino group contained in the diamine compound. .2 equivalents to 2 equivalents are preferable, and 0.3 equivalents to 1.2 equivalents are more preferable.

  The synthesis reaction is preferably performed in an organic solvent. The reaction temperature is preferably −20 ° C. to 150 ° C., more preferably 0 ° C. to 100 ° C. The reaction time is preferably 0.5 hours to 24 hours, and more preferably 2 hours to 12 hours.

  The organic solvent is not particularly limited as long as it can dissolve the synthesized polyamic acid. For example, N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide, N, N-dimethylformamide, N, N-dimethylimidazolidinone, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide, m-cresol, xylenol, phenol, halogenated phenol, diethylene glycol ethyl methyl ether and the like can be mentioned.

  As the usage-amount of an organic solvent, 0.1 mass part-50 mass parts are preferable with respect to 100 mass parts of total amounts of tetracarboxylic dianhydride and a diamine compound, and 5 mass parts-40 mass parts are more preferable.

  The polyamic acid solution obtained after the reaction may be used as it is for the preparation of the liquid crystal aligning agent, or may be used for the preparation of the liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution. You may use for preparation of a liquid crystal aligning agent, after refine | purifying an acid. Examples of the method for isolating the polyamic acid include a method of pouring a reaction solution into a large amount of a poor solvent and drying a precipitate obtained under reduced pressure, and a method of distilling the reaction solution under reduced pressure using an evaporator. Examples of the method for purifying the polyamic acid include a method in which the isolated polyamic acid is dissolved again in an organic solvent and precipitated with a poor solvent, and a method in which the step of distilling off the organic solvent or the like with an evaporator is performed once or a plurality of times. .

[Polyimide]
The polyimide can be produced by dehydrating and ring-closing the amic acid structure of the polyamic acid to imidize it. The polyimide may be a completely imidized product in which all of the amic acid structure of the precursor polyamic acid has been dehydrated and cyclized, and only a part of the amic acid structure may be dehydrated and cyclized to form an amic acid structure and an imide. It may be a partially imidized product in which a ring structure coexists.

  As a method for synthesizing polyimide, for example, (i) a method of heating a polyamic acid (hereinafter also referred to as “method (i)”), (ii) a polyamic acid is dissolved in an organic solvent, and a dehydrating agent and a dehydrating agent are dissolved in this solution. Examples thereof include a method by a dehydration ring-closing reaction of a polyamic acid, such as a method of adding a ring-closing catalyst and heating as necessary (hereinafter also referred to as “method (ii)”).

  As reaction temperature in method (i), 50 to 200 degreeC is preferable and 60 to 170 degreeC is more preferable. When the reaction temperature is less than 50 ° C., the dehydration ring-closing reaction does not proceed sufficiently, and when the reaction temperature exceeds 200 ° C., the molecular weight of the resulting polyimide may decrease. The reaction time is preferably 0.5 hours to 48 hours, and more preferably 2 hours to 20 hours.

  The polyimide obtained in the method (i) may be used for the preparation of the liquid crystal aligning agent as it is, may be used for the preparation of the liquid crystal aligning agent after isolating the polyimide, or may be obtained after purifying the isolated polyimide. You may use for the preparation of a liquid crystal aligning agent, after refine | purifying the polyimide obtained.

  Examples of the dehydrating agent in the method (ii) include acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride.

  Although the usage-amount of a dehydrating agent is suitably selected by the desired imidation rate, 0.01 mol-20 mol are preferable with respect to 1 mol of amic acid structures of a polyamic acid.

  Examples of the dehydration ring closure catalyst in the method (ii) include pyridine, collidine, lutidine, triethylamine and the like.

  The amount of the dehydration ring closure catalyst used is preferably 0.01 mol to 10 mol with respect to 1 mol of the dehydrating agent contained. In addition, the imidation rate can be increased as the content of the dehydrating agent and the dehydrating ring-closing agent is increased.

  Examples of the organic solvent used in the method (ii) include organic solvents similar to those exemplified as those used for the synthesis of polyamic acid.

  The reaction temperature in method (ii) is preferably 0 ° C to 180 ° C, more preferably 10 ° C to 150 ° C. The reaction time is preferably 0.5 hour to 20 hours, and more preferably 1 hour to 8 hours. By setting the reaction conditions in the above range, the dehydration ring-closing reaction proceeds sufficiently, and the molecular weight of the resulting polyimide can be made appropriate.

  In the method (ii), a reaction solution containing polyimide is obtained. This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, or after removing the dehydrating agent and the dehydrating ring-closing catalyst from the reaction solution, it may be used for the preparation of the liquid crystal aligning agent. You may use for preparation of an agent, or you may use for preparation of a liquid crystal aligning agent, after purifying the isolated polyimide. Examples of a method for removing the dehydrating agent and the dehydrating ring-closing catalyst from the reaction solution include a solvent replacement method. Examples of the polyimide isolation method and purification method include the same methods as those exemplified as the polyamic acid isolation method and purification method.

[(Meth) acrylic polymer]
[A] The (meth) acrylic polymer as the polymer is not particularly limited as long as it is a (meth) acrylic polymer containing a group represented by the above formula (1). It is obtained by polymerizing a compound by a known method. For example, (a) an epoxy group-containing ethylenically unsaturated compound (hereinafter also referred to as “(a) unsaturated compound”) and (b1) an ethylenically unsaturated carboxylic acid and / or a polymerizable unsaturated polyvalent carboxylic acid anhydride (Hereinafter also referred to as “(b1) unsaturated compound”) and (a) unsaturated compound and (b1) polymerizable unsaturated compound other than unsaturated compound (hereinafter also referred to as “(b2) unsaturated compound”) It can be obtained by polymerizing with a copolymer.

  (A) As unsaturated compounds, for example, glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, (meth) acrylic acid 3,4 -Epoxybutyl, 3,4-epoxybutyl α-ethyl acrylate, 6,7-epoxyheptyl (meth) acrylate, 6,7-epoxyheptyl α-ethyl acrylate, and the like.

(B1) Examples of unsaturated compounds include (meth) acrylic acid, crotonic acid, α-ethylacrylic acid, α-n-propylacrylic acid, α-n-butylacrylic acid, maleic acid, fumaric acid, citraconic acid, Unsaturated carboxylic acids such as mesaconic acid and itaconic acid;
Examples thereof include unsaturated polycarboxylic anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, and cis-1,2,3,4-tetrahydrophthalic anhydride.

(B2) Examples of unsaturated compounds include (meth) acrylic acid ester having a group represented by the above formula (1), 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and the like. Esters having a (meth) acrylic acid hydroxyl group;
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, (Meth) acrylic acid alkyl esters such as sec-butyl (meth) acrylate and t-butyl (meth) acrylate;
(Meth) acrylic acid cyclopentyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid 2-methylcyclohexyl, (meth) acrylic acid tricyclo [5.2.1.0 ^2,6 ] decan-8-yl, (meta ) (Meth) acrylic acid alicyclic esters such as 2-dicyclopentanyloxyethyl acrylate, isobornyl (meth) acrylate, cholestanyl (meth) acrylate;
(Meth) acrylic acid aryl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate;
Unsaturated dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
N-phenylmaleimide, N-benzylmaleimide, N-cyclohexylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Unsaturated dicarbonylimide derivatives such as maleimide propionate, N- (9-acridyl) maleimide;
Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide;
Unsaturated amide compounds such as (meth) acrylamide and N, N-dimethyl (meth) acrylamide;
Aromatic vinyl compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene;
Indene derivatives such as indene and 1-methylindene;
In addition to conjugated diene compounds such as 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene, vinyl chloride, vinylidene chloride, vinyl acetate, and the like can be given.

  (A) The unsaturated compound is preferably glycidyl (meth) acrylate, (b1) the unsaturated compound is preferably (meth) acrylic acid, and (b2) the unsaturated compound is preferably cholestanyl (meth) acrylate. . [A] When the (meth) acrylic polymer as a polymer is synthesized by radical polymerization, for example, from the viewpoint of introducing the group represented by the above formula (1) into the polymer, 1 It is necessary to use an unsaturated compound having at least a group represented by the above formula (1). On the other hand, for example, a group represented by the above formula (1) can be introduced by a conventionally known polymer reaction using an epoxy group in a polymer having no group represented by the above formula (1). .

  As a method for synthesizing the (meth) acrylic polymer, it is convenient to synthesize each unsaturated compound by, for example, radical polymerization in the presence of a suitable solvent and a polymerization initiator. As an organic solvent, the organic solvent similar to the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid, etc. are mentioned, for example.

Examples of the polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- (4-methoxy-2, Azo compounds such as 4-dimethylvaleronitrile);
Organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis- (t-butylperoxy) cyclohexane;
hydrogen peroxide;
Examples thereof include a redox initiator composed of these peroxides and a reducing agent. These polymerization initiators can be used alone or in admixture of two or more.

[Polysiloxane]
[A] The polysiloxane as the polymer is not particularly limited as long as it is a polysiloxane containing a group represented by the above formula (1), but for example, at least selected from the group consisting of alkoxysilane compounds and halogenated silane compounds One silane compound (hereinafter also referred to as “raw silane compound”) can be synthesized by hydrolysis or hydrolysis / condensation, preferably in the presence of water and a catalyst, in an appropriate organic solvent.

Examples of the raw material silane compound include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetra Chlorosilane, etc .;
Methyltrimethoxysilane, methyltriethoxysilane, octadecyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, methyltri-tert-butoxysilane, Methyltriphenoxysilane, methyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert -Butoxysilane, ethyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane and the like;
Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldichlorosilane, etc .;
Trimethylmethoxysilane, trimethylethoxysilane, trimethylchlorosilane, etc .;
Examples thereof include silane having a group represented by the above formula (1).

  Among these raw material silane compounds, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane, trimethyl Ethoxysilane, octadecyltriethoxysilane, and silane having a group represented by the above formula (1) are preferable. [A] When polysiloxane is selected as the polymer, from the viewpoint of introducing the group represented by the above formula (1) into the polymer, at least one represented by the above formula (1) as one of the raw material silane compounds. It is necessary to use a silane having the group

  Examples of the organic solvent that can be optionally used when synthesizing the polysiloxane include alcohol compounds, ketone compounds, amide compounds, ester compounds, and other aprotic compounds. These can be used alone or in combination of two or more.

  As reaction temperature at the time of synthesize | combining polysiloxane, 0 to 100 degreeC is preferable and 15 to 80 degreeC is more preferable. The reaction time is preferably 0.5 to 24 hours, and more preferably 1 to 8 hours.

[Polyamic acid ester]
The polyamic acid ester is a polymer obtained by reacting the above-described polyamic acid with an organic halide, alcohol or phenol.

  The [A] polymer is at least one polymer selected from the group consisting of polyamic acid, polyimide, (meth) acrylic polymer, polysiloxane, and polyamic acid ester. When a plurality of types of polymers are selected, high-speed response, which is a desired effect of the present application, can be realized if at least one type of polymer has a group represented by the above formula (1).

  [A] The weight average molecular weight (Mw) in terms of styrene by gel permeation chromatography of the polymer is not particularly limited, but in the case of polyamic acid, polyimide or polyamic acid ester, 1,000 to 500,000 is preferable, 2,000 to 300,000 is more preferable. In the case of a (meth) acrylic polymer, 1,000 to 1,000,000 is preferable, and 2,000 to 500,000 is more preferable. In the case of polysiloxane, 1,000 to 200,000 is preferable, and 2,000 to 100,000 is more preferable. By being in such a molecular weight range, it is possible to ensure good orientation and stability of the liquid crystal display element.

<Other optional components>
The liquid crystal aligning agent may contain other optional components such as a curing agent, a curing catalyst, a curing accelerator, an epoxy compound, and a surfactant as long as the effects of the present invention are not impaired. In addition, these other arbitrary components may use each component independently, and may mix and use 2 or more types. Moreover, the compounding quantity of another arbitrary component can be suitably determined according to the objective. Hereinafter, each component will be described in detail.

[Curing agent, curing catalyst and curing accelerator]
A hardening agent and a hardening catalyst can be contained in the liquid crystal aligning agent for the purpose of strengthening the crosslinking reaction of the [A] polymer. The curing accelerator can be contained in the liquid crystal aligning agent for the purpose of accelerating the curing reaction controlled by the curing agent.

  As the curing agent, a curing agent generally used for curing a curable compound having an epoxy group or a curable composition containing a compound having an epoxy group can be used. Examples of such a curing agent include polyvalent amines and polyvalent carboxylic acid anhydrides.

  Examples of the polyvalent carboxylic acid anhydride include cyclohexanetricarboxylic acid anhydride and other polyvalent carboxylic acid anhydrides. Examples of the cyclohexanetricarboxylic acid anhydride include, for example, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, cyclohexane-1,3,5-tricarboxylic acid-3,5-anhydride, cyclohexane-1,2 and the like. , 3-tricarboxylic acid-2,3-acid anhydride and the like. Examples of other polyvalent carboxylic acid anhydrides include 4-methyltetrahydrophthalic anhydride, methylnadic acid anhydride, dodecenyl succinic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, and the like. Can be mentioned.

  Examples of the curing catalyst include an antimony hexafluoride compound, a phosphorus hexafluoride compound, aluminum trisacetylacetonate, and the like. These catalysts can catalyze the cationic polymerization of epoxy groups by heating.

  Examples of the curing accelerator include imidazole compounds; quaternary phosphorus compounds; quaternary amine compounds; diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof; zinc octylate , Organometallic compounds such as tin octylate and aluminum acetylacetone complex; boron compounds such as boron trifluoride and triphenylborate; metal halogen compounds such as zinc chloride and stannic chloride; addition of dicyandiamide, amine and epoxy resin High melting point dispersion type latent curing accelerators such as amine addition type accelerators, etc .; microcapsule type latent curing accelerators coated with polymer on the surface of quaternary phosphonium salts, etc .; amine salt type latent curing accelerators Agents: High temperature dissociation type thermal cationic polymerization type latent curing accelerators such as Lewis acid salts and Bronsted acid salts.

[Epoxy compound]
The epoxy compound can be contained in the liquid crystal aligning agent from the viewpoint of improving the adhesion of the liquid crystal alignment film to be formed to the substrate surface.

  Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexanediol diester. Glycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N′-tetraglycidyl -M-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodi Enirumetan, N, N, - diglycidyl - benzylamine, N, N-diglycidyl - aminomethyl cyclohexane are preferred.

[Surfactant]
Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, polyalkylene oxide surfactants, and fluorine-containing surfactants.

<Method for preparing liquid crystal aligning agent>
The liquid crystal aligning agent contains the [A] polymer as an essential component as described above, and may contain other optional components as necessary. Preferably, each component is a solution composition in which each component is dissolved in an organic solvent. As prepared.

  As an organic solvent that can be used to prepare the liquid crystal aligning agent, those that dissolve the [A] polymer and other optional components and do not react with them are preferable. Examples of the organic solvent include the organic solvents exemplified above as those used for the synthesis of the polyamic acid. Moreover, you may use together the poor solvent illustrated as what is used for the synthesis | combination of a polyamic acid. These organic solvents may be used alone or in combination of two or more.

  As a preferable solvent used for the preparation of the liquid crystal aligning agent, each component contained in the liquid crystal aligning agent does not precipitate at a preferable solid content concentration described later, and the surface tension of the liquid crystal aligning agent is 25 mN / m to 40 mN /. The range is m.

  The solid content concentration of the liquid crystal aligning agent, that is, the ratio of the weight of all components other than the solvent in the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent is selected in consideration of viscosity, volatility, etc. Is in the range of 1% to 10% by weight. The liquid crystal aligning agent is applied to the substrate surface to form a coating film that becomes a liquid crystal aligning film. When the solid content concentration is 1% by mass or more, the film thickness of the coating film is less likely to be too small. A good liquid crystal alignment film can be obtained. On the other hand, when the solid content concentration is 10% by mass or less, it is possible to obtain an excellent liquid crystal alignment film while suppressing an excessive film thickness of the coating film. Moreover, it can prevent that the viscosity of a liquid crystal aligning agent increases, and can make an application | coating characteristic favorable. A more preferable range of the solid concentration is, for example, 1.5% by mass to 4.5% by mass in the case of the spinner method. In the case of the printing method, it is 3% by mass to 9% by mass. In the case of the ink jet method, the content is 1% by mass to 5% by mass.

<Liquid crystal display element>
The driving method of the liquid crystal display element of the present invention is not particularly limited, and TN, STN, IPS, FFS, Ht-VA (VA-IPS), VA (including VA-MVA method, VA-PVA method, etc.), etc. The present technology can be applied to various known systems, and includes the liquid crystal alignment film formed from the liquid crystal alignment agent. As described above, according to the liquid crystal aligning agent, it is possible to produce a liquid crystal display element capable of high-speed response and excellent in various performances such as voltage holding ratio, afterimage characteristics, uniform coating property, and light resistance. In general, a liquid crystal display element includes a pair of substrates on the surface of which a transparent electrode and a liquid crystal alignment film are laminated in this order, and the pair of substrates are disposed to face each other. Filled and the periphery is sealed with a sealant.

<Method for manufacturing liquid crystal display element>
The liquid crystal display element of this invention can be manufactured as follows, for example. The liquid crystal alignment film included in the liquid crystal display element is formed on the substrate by applying the liquid crystal alignment agent on the substrate and then heating the application surface. As the substrate, for example, glass such as float glass or soda glass; a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, alicyclic polyolefin, or the like can be used. A liquid crystal cell is manufactured by preparing two substrates on which a liquid crystal alignment film is formed as described above, and disposing a liquid crystal between the two substrates. Examples of the method for producing the liquid crystal cell include the following methods.

  As a first method, two substrates are arranged to face each other through a gap (cell gap) so that the respective liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded together using a sealant, A liquid crystal cell can be manufactured by injecting and filling liquid crystal into a cell gap defined by the substrate surface and a sealing agent, and then sealing the injection hole.

  As the second method, there is a method called an ODF (One Drop Fill) method. For example, an ultraviolet light curable sealing material is applied to a predetermined location on one of the two substrates on which the liquid crystal alignment film is formed, and liquid crystal is dropped on the liquid crystal alignment film surface. The other substrate is bonded so as to face each other, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant, whereby a liquid crystal cell can be manufactured.

  In any case, it is desirable to remove the flow alignment at the time of injection by heating to a temperature at which the liquid crystal using the liquid crystal cell takes an isotropic phase and then gradually cooling to room temperature. And the said liquid crystal display element can be obtained by bonding a polarizing plate on the outer surface of a liquid crystal cell.

  Examples of the sealing agent include an aluminum oxide sphere as a spacer and an epoxy resin containing a curing agent.

  As the liquid crystal, for example, a nematic liquid crystal, a smectic liquid crystal, or the like can be used. In the case of a TN liquid crystal cell or an STN liquid crystal cell, those having positive dielectric anisotropy for forming a nematic liquid crystal are preferable. Examples of such liquid crystals include biphenyl liquid crystals, phenyl cyclohexane liquid crystals, ester liquid crystals, terphenyl liquid crystals, biphenyl cyclohexane liquid crystals, pyrimidine liquid crystals, dioxane liquid crystals, bicyclooctane liquid crystals, and cubane liquid crystals. It is done. In addition, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonate, cholesteryl carbonate; chiral agents such as those sold under the trade names C-15 and CB-15 (Merck); p-decyloxybenzylidene- Ferroelectric liquid crystals such as p-amino-2-methylbutyl cinnamate can be further added and used.

  On the other hand, in the case of a vertical alignment type liquid crystal cell, a cell having negative dielectric anisotropy that forms a nematic liquid crystal is preferable. As such a liquid crystal, for example, a dicyanobenzene liquid crystal, a pyridazine liquid crystal, a Schiff base liquid crystal, an azoxy liquid crystal, a biphenyl liquid crystal, and a phenylcyclohexane liquid crystal are used.

  The polarizing plate used outside the liquid crystal cell is not particularly limited, but is a polarizing plate in which a polarizing film called an “H film” in which iodine is absorbed while stretching and aligning a polyvinyl alcohol film is sandwiched between cellulose acetate protective films, Or the polarizing plate etc. which consist of H film | membrane itself are mentioned.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

The weight average molecular weight (Mw) of the [A] polymer obtained in the following examples is a polystyrene conversion value measured by GPC having the following specifications.
Column: Tosoh Corporation, TSKgelGRCXLII
Solvent: Tetrahydrofuran Temperature: 40 ° C
Pressure: 68 kgf / cm ²

[Synthesis Example 1]
Compounds 1, 2, and 3 were synthesized according to the following reaction scheme.

  In a 500 mL three-necked flask equipped with a condenser, 12.6 g (0.0645 mol) of 4-cyano-4′-hydroxybiphenyl, 17.0 g (0.0717 mol) of 10-bromo-1-decanol, 28. 4 g and 350 mL of N, N-dimethylformamide were added, and the mixture was heated and stirred at 160 ° C. for 5 hours. After confirming the completion of the reaction by TLC, the reaction solution was cooled to room temperature. The reaction solution was poured into 1,000 mL of water and mixed and stirred. The precipitated white solid was filtered off and further washed with water. The obtained solid was vacuum-dried at 80 ° C. to obtain 20.6 g of the compound 1. Next, 20 g (0.0569 mol) of the obtained compound 1 was dissolved in 150 mL of dehydrated tetrahydrofuran (THF), 7.49 g (0.0740 mol) of triethylamine was added, and then dissolved in 150 mL of THF. 5-Dinitrobenzoyl chloride (14.4 g, 0.0625 mol) was gradually added dropwise over 30 minutes under ice cooling, and then stirred at room temperature for 3 hours. After completion of the reaction, triethylamine hydrochloride was removed by filtration, THF was removed by distillation under reduced pressure, and then 400 mL of chloroform was added. This solution was washed with water, the organic layer was dried over magnesium sulfate, and chloroform was removed by distillation under reduced pressure. Then, recrystallization was performed with ethanol, and 23.8 g of the compound 2 was obtained by vacuum drying at 80 ° C. Under a nitrogen stream, 20 g (0.0367 mol) of the above compound 2 and 1 g of 5% Pd / C (5 wt.% Relative to compound 2) were added to 500 mL of ethanol, and 4.2 g of 28% aqueous ammonia (compound 2) 2 times mole). While maintaining this solution at 15 ± 5 ° C., 21 g of hydrazine monohydrate (80% purity) was gradually added dropwise, and the reaction was allowed to stir for about 20 hours. Thereafter, the reaction solution was dropped into pure water while being filtered while hot, stirred and washed at room temperature, and then filtered to obtain a white to pale yellow solid. This was vacuum dried at 35 ° C. to obtain 16.8 g of the compound 3.

[Synthesis Example 2]
Compound 4 was synthesized according to the following reaction scheme.

  20 g (0.0569 mol) of Compound 1 obtained by the same operation as in Synthesis Example 1 was dissolved in 300 mL of THF, 7.49 g (0.0740 mol) of triethylamine was added, and then 6.53 g (0 of methacryloyl chloride). 0.0625 mol) was gradually added dropwise over 30 minutes under ice cooling, and then stirred at room temperature for 3 hours. After completion of the reaction, triethylamine hydrochloride was removed by filtration, THF was removed by distillation under reduced pressure, and then 400 mL of chloroform was added. This solution was washed with water, the organic layer was dried over magnesium sulfate, and chloroform was removed by distillation under reduced pressure. Then, recrystallization was performed with ethanol, and 17.7 g of the compound 4 was obtained by vacuum drying at 80 ° C.

[Synthesis Example 3]
Compounds 5 and 6 were synthesized according to the following reaction scheme.

  In a 500 mL three-necked flask equipped with a condenser tube, 12.6 g (0.0645 mol) of 4-cyano-4′-hydroxybiphenyl, 16.7 g (0.0717 mol) of 11-bromo-1-undecene, and 28. potassium carbonate. 4 g and 350 mL of N, N-dimethylformamide were added, and the mixture was heated and stirred at 160 ° C. for 5 hours. After confirming the completion of the reaction by TLC, the reaction solution was cooled to room temperature. The reaction solution was poured into 1,000 mL of water and mixed and stirred. The precipitated white solid was filtered off and further washed with water. The obtained solid was vacuum-dried at 80 ° C. to obtain 19.8 g of the compound 5. A 100 mL three-necked flask equipped with a reflux tube and a nitrogen introduction tube was charged with 8.69 g (0.0250 mol) of Compound 6, 15 g of trimethoxysilane and 40 μL of an isopropanol solution of 0.2 M chloroplatinic acid hexahydrate, After deaeration, the reaction was carried out under reflux for 10 hours under nitrogen. After passing the reaction mixture through a short column of silica gel, purification was performed with a silica column, and the solvent was removed to obtain 3.5 g of the above compound 6.

[Synthesis Example 4]
Compounds 7 to 11 were synthesized according to the following scheme.

  In a 500 mL three-necked flask equipped with a condenser tube, 12.5 g of 4- [difluoro (4-pentylcyclohexyl) methoxy] -2,3-difluorophenol, 10 g of 11-bromoundecanoate, 14.2 g of potassium carbonate, N, N -Dimethylformamide 200mL was added and it heat-stirred at 160 degreeC for 5 hours. After confirming the completion of the reaction by TLC, the reaction solution was cooled to room temperature. The reaction solution was put into 500 mL of water and mixed and stirred. The precipitated white solid was filtered off and further washed with water. The obtained solid was vacuum dried at 80 ° C. to obtain 14.8 g of Compound 7.

  To a 200 mL three-necked flask equipped with a condenser tube, 10 g of Compound 7, 1.6 g of lithium hydroxide monohydrate, 30 mL of methanol, and 15 mL of water were added, and the mixture was heated and stirred at 80 ° C. for 4 hours. After confirming the completion of the reaction by TLC, the reaction solution was cooled to room temperature. While stirring the reaction solution, dilute hydrochloric acid was slowly added dropwise to the reaction solution. The precipitated solid was filtered and washed with water and ethanol in this order. The obtained solid was vacuum dried at 80 ° C. to obtain 6 g of Compound 8.

  5 g of Compound 8 and 5 mL of thionyl chloride were mixed in a 100 mL three-necked flask equipped with a condenser, and the mixture was reacted by heating at 80 ° C. for 1 hour. The pressure was reduced with a water flow aspirator to remove unreacted thionyl chloride, and then mixed with 50 mL of tetrahydrofuran to obtain Solution (1). Next, 8.9 g of ethylene glycol, 20 mL of tetrahydrofuran, and 2.2 g of triethylamine were mixed in a 200 ml three-necked flask equipped with a dropping funnel and stirred in an ice bath. Solution (1) was added dropwise thereto, and the mixture was stirred at room temperature for 3 hours to be reacted. After the reaction, 300 mL of ethyl acetate was added, followed by washing with water by liquid separation purification. Thereafter, the organic layer was concentrated to obtain a solid. The obtained solid was recrystallized in ethanol / distilled water, and the precipitated solid was filtered and dried to obtain 4.3 g of Compound 9.

  In a 100 mL three-necked flask equipped with a dropping funnel, 4.0 g of Compound 9, 35 mL of tetrahydrofuran, and 1.0 g of triethylamine were stirred in an ice bath. 1.8 g of 3,5-dinitrobenzoyl chloride was slowly added dropwise thereto, and the mixture was stirred at room temperature for 3 hours to be reacted. After the reaction, 300 mL of ethyl acetate was added, and the mixture was washed with water by liquid separation purification. Thereafter, the organic layer was concentrated to obtain a solid. The obtained solid was recrystallized from ethanol, and the precipitated solid was filtered and dried to obtain 4.8 g of Compound 10.

  In a 100 mL three-necked flask equipped with a dropping funnel, 4 g of compound 10, 7 g of zinc, and 1.1 g of ammonium chloride were mixed, vacuum degassed, and purged with nitrogen. Next, 10 mL of tetrahydrofuran and 10 mL of ethanol were added and mixed with stirring in an ice bath. Next, 5 mL of distilled water was slowly added dropwise. The solvent used for the reaction was previously bubbled with nitrogen. During the dropping, the mixture was stirred while cooling in an ice bath, and then allowed to react at room temperature for 4 hours. Next, the reaction solution was filtered to remove the catalyst. Subsequently, 300 mL of ethyl acetate was added, and liquid separation purification was performed with distilled water. Subsequently, the organic layer was concentrated and the solvent was removed to obtain a solid. Crystallization was performed using ethanol, and the solid was filtered and dried under reduced pressure, followed by vacuum drying at 35 ° C. to obtain 2.4 g of Compound 11.

[Synthesis Example 5]
Compounds 12 to 14 were synthesized according to the following scheme.

  A 500 mL three-necked flask equipped with a condenser tube was mixed with 18.6 g of 3,5-dinitrofluorobenzene, 24.4 g of 11-bromoundecanol, 20 g of triethylamine, and 100 mL of tetrahydrofuran, and reacted at 100 ° C. for 30 hours in a nitrogen atmosphere. I let you. After the reaction, 200 mL of ethyl acetate was added, and liquid separation purification was performed 4 times with 50 mL of distilled water. Subsequently, the organic layer was concentrated and the solvent was removed to obtain a tan liquid. A small amount of ethanol was added thereto and cooled at 0 ° C. or lower to precipitate a solid. Next, 30 g of Compound 12 was obtained by filtering and drying the precipitated solid.

  In a 300 mL three-necked flask equipped with a condenser tube, 8.3 g of Compound 12, 6 g of 2,3-difluoro-4- (4-pentylcyclohexyl) phenol, 6 g of potassium carbonate, and 100 mL of dimethylformamide were mixed, and the mixture was mixed at 80 ° C. Reacted for hours. After confirming the completion of the reaction, 200 mL of ethyl acetate was added, and separation and purification was performed 4 times with 50 mL of distilled water. Subsequently, the organic layer was concentrated and the solvent was removed to obtain a tan liquid. A small amount of ethanol was added thereto and cooled at 0 ° C. or lower to precipitate a solid. Next, 10 g of Compound 13 was obtained by filtering and drying the precipitated solid.

  In a 200 mL three-necked flask equipped with a dropping funnel, 9.8 g of compound 13, 20 g of zinc, and 3.4 g of ammonium chloride were mixed, vacuum deaerated, and purged with nitrogen. Next, 30 mL of tetrahydrofuran and 30 mL of ethanol were added and mixed with stirring in an ice bath. Next, 10 mL of distilled water was slowly added dropwise. The solvent used for the reaction was previously bubbled with nitrogen. During the dropwise addition, the mixture was stirred while being cooled in an ice bath, and then reacted at room temperature for 6 hours. Next, the reaction solution was filtered to remove the catalyst. Subsequently, 300 mL of ethyl acetate was added, and liquid separation washing was performed with distilled water. Subsequently, the organic layer was concentrated and the solvent was removed to obtain a solid. 5g of compound 14 was obtained by recrystallizing with ethanol and filtering solid and drying under reduced pressure.

[Synthesis Example 6]
Compounds 15 to 17 were synthesized according to the following scheme.

  3.48 g of 3 ′, 4 ′, 5′-trifluoro-4-hydroxybiphenyl, 3.38 g of 2- [2- (2-chloroethoxy) ethoxy] ethanol, 8.3 g of potassium carbonate, and 100 mL of dimethylformamide were mixed. The mixture was reacted at 85 ° C. for 24 hours under a nitrogen atmosphere. Subsequently, 200 mL of ethyl acetate was added, and liquid separation purification was performed with distilled water. The organic layer was concentrated and the solvent was removed to obtain 6 g of Compound 15 (light yellow liquid).

  5 g of compound 15, 2.9 g of 2,4-dinitrofluorobenzene, 50 mL of tetrahydrofuran, and 1.9 g of triethylamine were mixed and reacted at 80 ° C. for 10 hours. 200 mL of ethyl acetate was added, and liquid separation purification was performed with distilled water. 4.8g of compound 16 was obtained by concentrating the organic layer and removing the solvent.

  In a 100 mL three-necked flask equipped with a dropping funnel, 4 g of Compound 16, 10 g of zinc, and 1.6 g of ammonium chloride were mixed, vacuum degassed, and purged with nitrogen. Next, under a nitrogen stream, 10 ml of tetrahydrofuran and 10 ml of ethanol were added and stirred and mixed in an ice bath. Next, 5 ml of distilled water was slowly added dropwise. The solvent used for the reaction was previously bubbled with nitrogen. During the dropping, the mixture was stirred while cooling in an ice bath, and then allowed to react at room temperature for 2 hours. Next, the reaction solution was filtered to remove the catalyst. Subsequently, 300 ml of ethyl acetate was added, and liquid separation purification was performed with distilled water. Subsequently, the organic layer was concentrated and the solvent was removed to obtain a solid. Recrystallization with ethanol was performed, and the solid was filtered and dried under reduced pressure, followed by drying, and 3.3 g of Compound 17 was obtained.

[Synthesis Example 7]
Compounds 18 and 19 were synthesized according to the following scheme.

  4- [difluoro (4-pentylcyclohexyl) methoxy] -2,3-difluorophenol 50 g, 11-bromoundecanol 38 g, potassium carbonate 60 g, and dimethylformamide 100 mL were mixed and reacted at 85 ° C. for 24 hours in a nitrogen atmosphere. I let you. Subsequently, 200 mL of ethyl acetate was added, and liquid separation purification was performed with distilled water. The organic layer was concentrated and the solvent was removed to obtain 38.7 g of Compound 18.

  10 g of compound 18 was dissolved in 20 mL of tetrahydrofuran, 3.9 g of triethylamine was added, and then a solution of 2.6 g of acrylic acid chloride dissolved in 10 mL of tetrahydrofuran was gradually added dropwise over 15 minutes under ice cooling, and then room temperature. For 2 hours. After completion of the reaction, triethylamine hydrochloride was removed by filtration, the solvent was removed by distillation under reduced pressure, and then 400 mL of chloroform was added. This solution was washed with water, the organic layer was dried over magnesium sulfate, and chloroform was removed by distillation under reduced pressure. Then, recrystallization was performed with ethanol, and 11 g of Compound 19 was obtained by vacuum drying at 80 ° C.

<[A] Synthesis of polymer>
[Synthesis of polyamic acid]
[Synthesis Example 8]
26.08 g of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 7.90 g of diamine (G-1) represented by the following formula and 66.0 g of the diamine of the above compound 3 were dissolved in 400 g of NMP, For 6 hours. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40 ° C. under reduced pressure for 15 hours to obtain 78.5 g of polyamic acid (PA-1).

[Synthesis Example 9]
100.1g of polyamic acid (PA-2) was obtained by operating like the synthesis example 8 except having used 96.6g of compounds 11 instead of the compound 3.

[Synthesis of polyimide]
[Synthesis Example 10]
Tetracarboxylic dianhydride 2,3,5-tricarboxycyclopentylacetic dianhydride 13.45 g, diamine compound 3,5-diaminobenzoic acid 3.72 g, diamine represented by the following formula (G-2) 3.02 g and 14.81 g of the diamine of Compound 3 were dissolved in 140 g of NMP and reacted at 60 ° C. for 4 hours. When the viscosity of this polymerization liquid was measured, it was 2,200 mPa · s. The reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, it was washed with methyl alcohol and dried at 40 ° C. under reduced pressure for 24 hours to obtain a polyamic acid. All of the obtained polyamic acid was redissolved in 465 g of NMP, 7.12 g of pyridine and 9.19 g of acetic anhydride were added, dehydration and cyclization were carried out at 110 ° C. for 4 hours, and precipitation, washing and drying under reduced pressure were carried out in the same manner as above. 21.5 g of polyimide (PI-1) having an imidation ratio of 68% was obtained.

[Synthesis Example 11]
Dissolve 10.89 g of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride, 7.33 g of the above diamine (G-2) and 16.78 g of diamine of compound 3 in NMP as diamine compounds. , Reacted at 60 ° C. for 4 hours. When the viscosity of this polymerization liquid was measured, it was 1,250 mPa · s. The reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, it was washed with methyl alcohol and dried at 40 ° C. under reduced pressure for 24 hours to obtain a polyamic acid. All of the obtained polyamic acid was redissolved in 465 g of NMP, 3.84 g of pyridine and 4.96 g of acetic anhydride were added, dehydration and ring closure were carried out at 110 ° C. for 4 hours, and precipitation, washing and drying under reduced pressure were carried out in the same manner as above. As a result, 23.1 g of polyimide (PI-2) having an imidization ratio of 49% was obtained.

[Synthesis Example 12]
2.17 g of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride, 3.60 g of the diamine (G-1) as a diamine compound, 6.68 g and 4,4 ′ of diamine of compound 3 -Diaminodiphenylmethane 9.55g was dissolved in NMP140g, and it was made to react at 60 degreeC for 4 hours. When the viscosity of this polymerization liquid was measured, it was 2,700 mPa · s. The reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, it was washed with methyl alcohol and dried at 40 ° C. under reduced pressure for 24 hours to obtain a polyamic acid. All of the obtained polyamic acid was redissolved in 465 g of NMP, 10.70 g of pyridine and 13.82 g of acetic anhydride were added, dehydration and ring closure were carried out at 110 ° C. for 4 hours, and precipitation, washing and drying under reduced pressure were carried out in the same manner as above. 22.4 g of polyimide (PI-3) having an imidation ratio of 76% was obtained.

[Synthesis Example 13]
By operating in the same manner as in Synthesis Example 10 except that 7.69 g of compound 14 was used instead of compound 3, 22.9 g of polyimide (PI-4) having an imidization ratio of 76% was obtained.

[Synthesis Example 14]
By operating in the same manner as in Synthesis Example 10 except that 6.36 g of Compound 17 was used instead of Compound 3, 21.9 g of polyimide (PI-5) having an imidization ratio of 76% was obtained.

[Synthesis of methacrylic polymer]
[Synthesis Example 15]
Cholestanyl methacrylate was synthesized according to the following reaction scheme.

  80 g of β-cholestanol was dissolved in 800 mL of THF, 27.2 g of triethylamine was added, 35.6 g of methacryloyl chloride was gradually added dropwise, and the mixture was stirred at room temperature for 3 hours. After completion of the reaction, triethylamine hydrochloride was removed by filtration, THF was removed by distillation under reduced pressure, and then 400 mL of chloroform was added. This solution was washed with water, the organic layer was dried over magnesium sulfate, and chloroform was removed by distillation under reduced pressure. Thereafter, recrystallization with ethanol was performed to obtain 54 g (yield: 57.4%) of cholestanyl methacrylate as a white solid shown in the above reaction formula. The above-mentioned cholestanyl methacrylate 15.16 g (0.033 mol), glycidyl methacrylate 12.8 g (0.09 mol), methacrylic acid 7.2 g as monomers in a four-necked flask equipped with a stir bar, three-way cock and thermometer (0.084 mol) and 45.85 g (0.109 mol) of the above compound 4, 52.8 g of diethylene glycol ethyl methyl ether as a solvent, and 2,2′-azobis (2,4-dimethylvaleronitrile as a polymerization initiator) ) 2.24 g and 0.96 g of α-methylstyrene dimer as a chain transfer agent were added. This was bubbled with a nitrogen stream for about 10 minutes to perform nitrogen substitution in the system, and then reacted at 70 ° C. for 5 hours in a nitrogen atmosphere to obtain a methacrylic polymer (PM-1). When the molecular weight of the methacrylic polymer (PM-1) was measured by GPC, Mw = 96,000 and Mw / Mn = 7.87, and no peak attributable to the residual monomer was observed. In the polymer solution, it was assumed that the charged monomers were all converted to methacrylic polymer (PM-1) and diluted as they were to prepare the liquid crystal aligning agent of the present invention.

[Synthesis Example 16]
10.0 g (0.0219 mol) of cholestanyl methacrylate, 15.0 g (0.1055 mol) of glycidyl methacrylate, 9.0 g (0.1045 mol) of methacrylic acid and 19.3 g (0.046 mol) of compound 4 Preparation, 43.0 g of diethylene glycol ethyl methyl ether as a solvent, 1.83 g of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator and 0.78 g of α-methylstyrene dimer as a chain transfer agent were used. Was operated in the same manner as in Synthesis Example 15 to obtain a methacrylic polymer (PM-2). When the molecular weight of the methacrylic polymer (PM-2) was measured by GPC, Mw = 12,500 and Mw / Mn = 9.54, and no peak attributable to the residual monomer was observed. In this polymer solution, it was assumed that the charged monomers were all converted to methacrylic polymer (PM-2), and diluted as they were to prepare the liquid crystal aligning agent of the present invention.

[Synthesis Example 17]
A methacrylic polymer (PM-3) was obtained in the same manner as in Synthesis Example 16 except that 25.6 g (0.046 mol) of Compound 19 was used instead of Compound 4. When the molecular weight of the methacrylic polymer (PM-3) was measured by GPC, Mw = 131,000 and Mw / Mn = 9.43, and no peaks attributable to residual monomers were observed. In this polymer solution, it was assumed that the charged monomers were all converted to methacrylic polymer (PM-3) and diluted as they were to prepare the liquid crystal aligning agent of the present invention.

[Synthesis of polysiloxane]
[Synthesis Example 18]
A reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser was charged with 12.4 g of oxalic acid and 22.2 g of ethanol, and stirred to prepare an ethanol solution of oxalic acid. Next, this solution was heated to 70 ° C. in a nitrogen atmosphere, and then a mixture of 11.1 g of tetraethoxysilane and 10.6 g of compound 6 was added dropwise thereto as a silane compound as a raw material. After completion of the dropwise addition, the temperature of 70 ° C. was maintained for 6 hours and then cooled to 25 ° C., and then 40.0 g of butyl cellosolve was added to prepare a solution containing polyorganosiloxane (PS-1). Mw of polyorganosiloxane (PS-1) contained in this solution was 9,000.

[Synthesis Example 19]
Into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 13.9 g of oxalic acid and 19.5 g of ethanol were added and stirred to prepare an ethanol solution of oxalic acid. Next, this solution was heated to 70 ° C. in a nitrogen atmosphere, and then a mixture of 15.1 g of tetraethoxysilane and 3.95 g of compound 6 was dropped as a raw material silane compound. After completion of the dropwise addition, the temperature of 70 ° C. was maintained for 6 hours and then cooled to 25 ° C., and then 40.0 g of butyl cellosolve was added to prepare a solution containing polyorganosiloxane (PS-2). Mw of polyorganosiloxane (PS-2) contained in this solution was 12,000.

[Synthesis Example 20]
A reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser was charged with 10.2 g of oxalic acid and 26.3 g of ethanol and stirred to prepare an ethanol solution of oxalic acid. Next, this solution was heated to 70 ° C. under a nitrogen atmosphere, and then a mixture of 5.54 g of tetraethoxysilane, 12.49 g of compound 6 and 2.5 g of octadecyltriethoxysilane was added dropwise as a raw material silane compound. did. After completion of the dropwise addition, the temperature of 70 ° C. was maintained for 6 hours and then cooled to 25 ° C., and then 40.0 g of butyl cellosolve was added to prepare a solution containing polyorganosiloxane (PS-3). Mw of polyorganosiloxane (PS-3) contained in this solution was 6,000.

[Synthesis Example 21]
19.88 g of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride, 6.83 g of p-phenylenediamine, 3.58 g of diaminodiphenylmethane as the diamine compound, and the above diamine (G-1) 4. 72 g was dissolved in 140 g of NMP and reacted at 60 ° C. for 4 hours. When the viscosity of this polymerization liquid was measured, it was 2,100 mPa · s. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, it was washed with methyl alcohol and dried at 40 ° C. under reduced pressure for 24 hours to obtain 32.8 g of polyamic acid. 30 g of the resulting polyamic was dissolved in 400 g of NMP, 12.0 g of pyridine and 15.5 g of acetic anhydride were added, dehydration and ring closure were performed at 110 ° C. for 4 hours, precipitation, washing and drying under reduced pressure were performed in the same manner as above, and the imidization rate 25 g of 79% polyimide (PI-6) was obtained.

[Synthesis Example 22]
Cholestanyl methacrylate 15.16 g (0.0332 mol), glycidyl methacrylate 12.8 g (0.09 mol), methacrylic acid 7.2 g (monomer) in a four-necked flask set with a stir bar, three-way cock, and thermometer 0.0836 mol), 7.2 g (0.0691 mol) of styrene and 7.2 g (0.0402 mol) of N-cyclohexylmaleimide, 52.8 g of diethylene glycol ethyl methyl ether as a solvent, 2, 2.24 g of 2′-azobis (2,4-dimethylvaleronitrile) and 0.96 g of α-methylstyrene dimer as a chain transfer agent were added. This was bubbled in a nitrogen stream for about 10 minutes to perform nitrogen substitution in the system, and then reacted at 70 ° C. for 5 hours in a nitrogen atmosphere to obtain a methacrylic polymer (PM-4) having a pretilt angle developing component. . When the molecular weight of the methacrylic polymer (PM-4) was measured by GPC, Mw = 96,000 and Mw / Mn = 7.87, and no peak attributable to the residual monomer was observed. In this polymer solution, it was assumed that the charged monomers were all converted to methacrylic polymer (PM-4) and diluted as they were to prepare the liquid crystal aligning agent of the present invention.

[Synthesis Example 23]
A reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser was charged with 10.2 g of oxalic acid and 26.3 g of ethanol and stirred to prepare an ethanol solution of oxalic acid. Next, this solution was heated to 70 ° C. in a nitrogen atmosphere, and then a mixture of 11.1 g of tetraethoxysilane and 2.5 g of octadecyltriethoxysilane was added dropwise thereto as a raw material silane compound. After completion of the dropping, the temperature of 70 ° C. was maintained for 6 hours and then cooled to 25 ° C., and then 40.0 g of butyl cellosolve was added to prepare a solution containing polyorganosiloxane (PS-4). Mw of the polyorganosiloxane (PS-4) contained in this solution was 6,900.

<Preparation of liquid crystal aligning agent>
[Example 1]
NMP and butyl cellosolve are added to the polyamic acid (PA-1) so that the solvent composition is NMP: butyl cellosolve = 50: 50 (mass ratio), and the solid content concentration is 3.5% by mass (for liquid crystal cell preparation) and A solution having a solid concentration of 7.0% (for uniform coating property evaluation) was obtained. After sufficiently stirring these solutions, a liquid crystal aligning agent (S-1) was prepared by filtering through a filter having a pore size of 0.2 μm.

[Example 2]
The liquid crystal aligning agent (S-2) was prepared by operating like Example 1 except having used the said polyamic acid (PA-2) instead of the said polyamic acid (PA-1).

[Example 3]
NMP and butyl cellosolve are added to the polyimide (PI-1) so that the solvent composition is NMP: butyl cellosolve = 50: 50 (mass ratio), and the solid content concentration is 3.5% by mass (for liquid crystal cell preparation) and solids. A solution having a partial concentration of 7.0% (for uniform coating property evaluation) was obtained. After sufficiently stirring these solutions, a liquid crystal aligning agent (S-3) was prepared by filtering through a filter having a pore size of 0.2 μm.

[Example 4]
NMP and butyl cellosolve are added to the polyimide (PI-2) so that the solvent composition is NMP: butyl cellosolve = 50: 50 (mass ratio), and the solid content concentration is 3.5% by mass (for liquid crystal cell preparation) and solids. A solution having a partial concentration of 7.0% (for uniform coating property evaluation) was obtained. After sufficiently stirring these solutions, a liquid crystal aligning agent (S-4) was prepared by filtering through a filter having a pore size of 0.2 μm.

[Example 5]
NMP and butyl cellosolve are added to the polyimide (PI-3) so that the solvent composition is NMP: butyl cellosolve = 70: 30 (mass ratio), and the solid content concentration is 3.5% by mass (for liquid crystal cell preparation) and solids. A solution having a partial concentration of 7.0% (for uniform coating property evaluation) was obtained. After sufficiently stirring these solutions, a liquid crystal aligning agent (S-5) was prepared by filtering through a filter having a pore size of 0.2 μm.

[Example 6]
The liquid crystal aligning agent (S-6) was prepared by operating like Example 3 except having used the said polyimide (PI-4) instead of the said polyimide (PI-1).

[Example 7]
A liquid crystal aligning agent (S-7) was prepared by operating in the same manner as in Example 3 except that the polyimide (PI-5) was used instead of the polyimide (PI-1).

[Example 8]
Diethylene glycol methyl ethyl ether was further added to the methacrylic polymer (PM-1) solution, the solid content concentration was 3.5% by mass (for liquid crystal cell preparation), and the solid content concentration was 7.0% (for uniform coating property evaluation). ) Solution. After sufficiently stirring these solutions, each was filtered using a filter having a pore diameter of 0.2 μm to prepare a liquid crystal aligning agent (S-8).

[Example 9]
Diethylene glycol methyl ethyl ether was further added to the methacrylic polymer (PM-2) solution, the solid content concentration was 3.5% by mass (for liquid crystal cell preparation), and the solid content concentration was 7.0% (for uniform coating property evaluation). ) Solution. After sufficiently stirring these solutions, each was filtered using a filter having a pore diameter of 0.2 μm to prepare a liquid crystal aligning agent (S-9).

[Example 10]
The liquid crystal aligning agent (S-10) was prepared by operating like Example 8 except having used the said methacrylic polymer (PM-3) instead of the said methacrylic polymer (PM-1).

[Example 11]
A solution containing butyl cellosolve in a solution containing the polyorganosiloxane (PS-1) and having a solid content concentration of 5% by weight (for liquid crystal cell preparation) and a solid content concentration of 10.0% (for evaluation of uniform coating properties) did. After sufficiently stirring these solutions, a liquid crystal aligning agent (S-11) was prepared by filtering using a filter having a pore diameter of 1 μm.

[Example 12]
Butyl cellosolve is added to the solution containing the polyorganosiloxane (PS-2), and a solution having a solid content concentration of 5% by weight (for liquid crystal cell preparation) and a solid content concentration of 10.0% (for uniform coating property evaluation) did. After sufficiently stirring these solutions, a liquid crystal aligning agent (S-12) was prepared by filtering using a filter having a pore diameter of 1 μm.

[Example 13]
Butyl cellosolve is added to the solution containing the polyorganosiloxane (PS-3), and a solution having a solid content concentration of 5% by weight (for liquid crystal cell preparation) and a solid content concentration of 10.0% (for uniform coating property evaluation) did. After sufficiently stirring these solutions, a liquid crystal aligning agent (S-13) was prepared by filtering using a filter having a pore diameter of 1 μm.

[Comparative Example 1]
NMP and butyl cellosolve were added to the polyimide (PI-6) so that the solvent composition was NMP: butyl cellosolve = 50: 50 (mass ratio), respectively, and the solid content concentration was 3.5% by mass (for liquid crystal cell preparation) and A solution having a solid concentration of 7.0% (for uniform coating property evaluation) was obtained. After sufficiently stirring these solutions, a liquid crystal aligning agent (CS-1) was prepared by filtering through a filter having a pore size of 0.2 μm.

[Comparative Example 2]
Diethylene glycol methyl ethyl ether was further added to the methacrylic polymer (PM-4) solution, the solid content concentration was 3.5% by mass (for liquid crystal cell preparation), and the solid content concentration was 7.0% (for uniform coating property evaluation). ) Solution. After sufficiently stirring these solutions, a liquid crystal aligning agent (CS-2) was obtained by filtering using a filter having a pore diameter of 0.2 μm.

[Comparative Example 3]
Add a butyl cellosolve to the solution containing the polyorganosiloxane (PS-4), and a solution having a solid content concentration of 5% by weight (for liquid crystal cell preparation) and a solid content concentration of 10.0% (for uniform coating property evaluation) did. After sufficiently stirring these solutions, a liquid crystal aligning agent (CS-3) was prepared by filtering using a filter having a pore diameter of 1 μm.

<Manufacture of liquid crystal display elements>
Each prepared liquid crystal aligning agent was applied on the transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film using a spinner, pre-baked on an 80 ° C. hot plate for 1 minute, and then replaced with nitrogen. By heating at 200 ° C. for 1 hour to remove the solvent, a coating film (liquid crystal alignment film) having a thickness of 0.08 μm was formed. This operation was repeated to produce a pair (two) of substrates having a liquid crystal alignment film. After applying an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 3.5 μm to the outer periphery of the surface having one liquid crystal alignment film of the above substrates by screen printing, the liquid crystal alignment film surfaces of the pair of substrates are made to face each other. The adhesive was heat cured by heating at 150 ° C. for 1 hour. Next, after filling negative liquid crystal (Merck, MLC-6608) into the gap between the substrates from the liquid crystal injection port, the liquid crystal injection port is sealed with an epoxy adhesive, and further, the flow alignment at the time of liquid crystal injection is removed. This was heated at 150 ° C. for 10 minutes and then gradually cooled to room temperature. Furthermore, a liquid crystal display element was manufactured by bonding a polarizing plate on both outer surfaces of the substrate so that the polarization directions of the two polarizing plates were orthogonal to each other.

<Evaluation>
The manufactured liquid crystal display element was evaluated as follows. The results are shown in Table 1.

[Response speed (msec.)]
The response speed (the rise time of the liquid crystal response) was measured with an apparatus including a polarizing microscope, a photodetector, and a pulse generator. Here, the liquid crystal response speed is the time (msec) required to change from 10% transmittance to 90% transmittance when a voltage of 5 V is applied to the manufactured liquid crystal display element from a state where no voltage is applied for a maximum of 1 second. .)

[Voltage holding ratio (%)]
A voltage of 5 V was applied to the liquid crystal display device manufactured above for 60 microseconds with a 167 millisecond span, and then the voltage holding ratio (%) after 167 milliseconds from the release of application was measured. The measuring device used was VHR-1 manufactured by Toyo Technica.

[Afterimage characteristics (mV)]
For a liquid crystal display device manufactured by operating in the same manner as described above, a voltage of 17 V DC was applied for 20 hours at an environmental temperature of 100 ° C., and the voltage remaining in the liquid crystal cell immediately after the DC voltage was turned off (residual DC voltage (mV )) Was determined by the flicker elimination method.

[Uniform coating properties]
A resin spacer (Sekisui Chemical Co., Ltd., Micropearl EX-0041-AC4) with a diameter of about 4.1 μm is sprayed on a 6-inch silicon wafer, and heat-treated for 10 minutes on a hot plate set at 120 ° C. A silicon wafer was prepared. Further, in the liquid crystal aligning agent composition, a liquid crystal aligning agent (solid content concentration: 7.0% to 10.0%) prepared for printing is attached with the above-mentioned fixing spacer using a liquid crystal aligning film printer (Nissha Printing Co., Ltd.). It was applied to a silicon wafer, pre-baked on a hot plate at 80 ° C. for 1 minute to remove the solvent, and then post-baked on a hot plate at 200 ° C. for 10 minutes to form a coating film having an average film thickness of 800 mm. This coating film was observed with a microscope having a magnification of 20 times, and the uniform coating property was evaluated. Evaluation was performed based on the presence or absence of repellency in the printing unevenness and the fixed spacer portion, and “A” (determined to be excellent) where no unevenness of printing unevenness and repellency in the fixing spacer portion was observed, “B” (determined as good) was judged that there was no coating failure, and “C” (determined as defective) was observed in either one of the printing unevenness and the repelling of the fixed spacer portion.

[Light resistance]
The voltage holding ratio after irradiation for 3,000 hours was measured in the same manner as described above with a weather meter using a carbon arc as a light source, and the amount of change in voltage holding ratio was 0.5% or less compared to the measured value before irradiation. Case "A" (determined as excellent), case exceeding 0.5% and 1% or less as "B" (determined as good), case exceeding 1% and 3% or less as "C" (somewhat good) And “D” (determined as defective).

  As is clear from the results in Table 1, the liquid crystal display elements including the liquid crystal alignment films formed using the liquid crystal alignment agents of Examples 1 to 13 exhibited good liquid crystal response speed. A liquid crystal display device comprising a liquid crystal alignment film formed from the liquid crystal alignment agent containing polyimide or polysiloxane showed a high voltage holding ratio. Moreover, the liquid crystal aligning agent containing a polyamic acid or a methacrylic polymer showed excellent uniform coatability. Furthermore, the liquid crystal display element provided with the liquid crystal aligning film formed from the said liquid crystal aligning agent containing polysiloxane or polyamic acid showed the afterimage characteristic which was excellent. A liquid crystal display device provided with a liquid crystal alignment film formed from the liquid crystal alignment agent containing polysiloxane exhibited excellent light resistance. Accordingly, the liquid crystal aligning agent enables high-speed response of the liquid crystal display element, and by appropriately selecting the polymer main chain structure, desired characteristics (voltage holding ratio, afterimage characteristics, uniform coating property, light resistance) are further improved. It can be excellent.

  According to the present invention, a liquid crystal aligning agent capable of high-speed response and capable of producing a liquid crystal display element excellent in various performances such as voltage holding ratio, afterimage characteristics, light resistance and the like, and excellent in uniform coating property. Can be provided. Therefore, the liquid crystal display element can be suitably applied in driving modes such as TN, STN, IPS, FFS, Ht-VA (VA-IPS), and VA (including MVA, PVA, optical vertical alignment, PSA, and the like). it can.

Claims (3)

[A] It contains at least one polymer selected from the group consisting of polyamic acid, polyimide and polyamic acid ester, and the polymer has a partial structure derived from a compound represented by the following formula (4) Liquid crystal aligning agent.

(In formula (4),
R ¹ is a methylene group, an alkylene group having 2 to 30 carbon atoms, — (C _{b ′} H _{2b ′} O) _{c ′} —, a phenylene group or a cyclohexylene group. b 'is an integer of 0-20. c 'is an integer of 0-10. However, some or all of the hydrogen atoms of these groups may be substituted.
R ² is a linking group containing a carbon-carbon double bond, a carbon-carbon triple bond, an ether bond, an ester bond or an amide bond.
R ³ is a group represented by the following formula (2).
a is 1.
R ⁹ is a single bond, —O—, * —COO— or —OCO—. However, * is a site | part couple | bonded with a diaminophenyl group.
d is 0 or 1.
e is an integer of 0-2.
g is 2 or 3. )

(In the formula (2),
R ⁴ and R ⁶ are each independently a phenylene group, a biphenylene group, a naphthalene group, a cyclohexylene group, a bicyclohexylene group, a cyclohexylenephenylene group, or a heterocyclic ring. However, some or all of the hydrogen atoms of these groups may be substituted.
R ⁵ is a linking group containing a methylene group, an alkylene group having 2 to 10 carbon atoms, a carbon-carbon double bond, a carbon-carbon triple bond, an ether bond, an ester bond or a heterocyclic ring. However, one part or all part of the hydrogen atom of the said coupling group may be substituted.
R ⁷ is a hydrogen atom, a cyano group, a fluorine atom, a trifluoromethyl group, an alkoxycarbonyl group, an alkyl group, an alkoxy group, a trifluoromethoxy group, or an alkylcarbonyloxy group.
b is 0 or 1. c is an integer of 1-9. However, when R ⁷ is plural, a plurality of R ⁷ may be the same or different. ) The liquid crystal aligning film formed from the liquid crystal aligning agent of Claim 1 . A liquid crystal display element provided with the liquid crystal aligning film of Claim 2 .